Alkyleneamine polymers containing nitroformate groups



United States Patent "ice Patented .312212 3,401,156 I Example II ALKYLENEAMINE POLYMERS CONTAINING Polyethylenermme, NITROFORMATE GROUPS H John R. Lovett, Edison, and Anthony J. Passannante,

Metuchen, N.J., assignors to Esso Research and Engi- 5 (-CHr-OHzN)s neering Company, a corporation of Delaware N0 Drawing Filed Feb 17 1961 Ser No 90 144 is commercially available and offers an attractive route 9 Claims. (CL to polymers containing a high proportion of N0 groups.

- Reaction of polyethyleneimine with nitroform was car- This invention relates to a high nitro content ried out by mixing a stoichiometrical proportion of nitropound d b ti a l m f an l fi i amine 10 form to react with the amlne groups at a reaction temor imine with nitroform, HC(NO perature of C. using water as diluent. The nitro- The polymeric reactants containing amino groups formate salt formed was recovered by decanting the which can be used are represented by the following: supernatant liquid and vacuum drying the residue. The

CHzNHz (CH2 CH)n (CHg(|3H)n (CHzOHzI |I)n -(CH21?'),.

NHz NH; NH:

CHINE; fl) (CH2- (-CHz-CH) (NCH2CH2)|1 (CNH-NH-)u HzNHz NHNH; H

For the sake of brevity these compounds are named as 25 nitroformate product was a solid which analyzed reapolyalkenyl-amines, since the monomeric hydrocarbon sonably well for the desired product: group is typified by the ethenyl group (CH CH (CHFCHPN )H and the amine substituent function. The term amine or amino is used generically to include the imine substituent C(Nom function (:NH) and hydrazino function (NH-NH-), N eale 28,8% Fou d 275%, and the like. The subscript 11 indicates that a number of the recurring units are linked together.

The polyalkenylamine nitroformates are interesting and useful compounds. They are easily prepared salts of nitroform. These salts may be made to contain a high The yellow polyethyleneimine nitroformate was also analyzed by an ultraviolet spectroscopic method which indicated it to have the requisite amount of nitroformate 1011.

ratio of nitro groups to carbon atoms thus making them Example In potent oxygen sources. These salts have reasonable ther- Polyethylenehydrazine nitroformate was prepared by mal stability. Studieshave shown that stabilizers can reaction of polyethylene hydrazine with nitroform in make these salts of practical value as rocket propellant either water or methanol. The nitroformate salt of the binders. i polymer was obtained as a yellow solid which on warm- -Although the polyalkenylamine nitroformates when ing and standing turned to an oil. The salt analyzed as formed are as a class amorphous powders when dry, the following product:

they are easily plasticized to rubbery materials having suitable tensile strength and elasticity. Their high NO C 2 ratio permits their use in high proportions, e.g. up to 30 2- 2)s vol.- percent in propellant systems that are required to N ca1c Found {meet high Specific imPulse requlrements, Values Stability tests run on the polymeric salts showed a relam theyange of ab011t28 to 9- tive stability of 1 n 111. Other stability studies indi- YP new polyalkenylamme P u whlch have 50 cated that the polyalkenylamine nitroformate salts of been Preparefl1 a Polyvmylamme mtroformatei an increased stability are the salts of polymers having an polyethylePe'lmme mtroformate and (In) Polyethyl amino group attached to a primary carbon. An example enehydrazme mtroformateg g of a polyalkenylamine nitroformate of high stability may Example I be polyallylamine nitroformate. Other polymer nitroformate structures of high stability are represented by Polyvinylamine was prepared as a hydrobromide salt the following structures:

according to the directions of. Reynolds & Kenyon (JACS, 69, 911 (1947)). The hydrobromide was con- CH NHHC NO OH NHHC NO verted to the nitroformate by the reaction of' nitroform a 2 m 2 z m and an aqueous solution of the hydrobromide from CH CH (GET )n which the product separated. The aqueous supernatant H2NH2-HC(NO2)3 Grimm-Homo, liquid was decanted off and the solid residuewas taken IV V up in acetone and precipitated by the addition of chloroform. A bright yellow solid product having a melting The Rolyalkenylamlfle nltfpfofmates 0 ta1ned are point of 135 C. was obtained. The structure for the characterlzed as Polymers having a Packbone Chain of polyvinylamine nitroformate salts is the following: Carbon atoms or of both carbon and nitrogen atoms, each recurring monomeric unit containing from 1 to 4 C atoms 2- n and 1 to 4 amino N atoms to which are attached 1 to 4 NHE'HWNOW HC(NO moieties. Typical compositional formulae for J the reacted monomeric units and polymeric compounds correspond to the following:

The most common and average composition is approximately:

C3H6N4O6 The polyalkenylamine nitroformates, preferably plasticized, are useful as binders to impart strength and rigidity to composites of fuels and oxidizers. Powdered metals, e.g. boron, aluminum, magnesium, beryllium, and lithium may be used as fuels. Compounds containing nitro groups, e.g. hexnitroethane, ammonium perchlorate, nitronium perchlorate may be added as oxygen oxidizers. Difluoramino compounds, e.g. tetrakis (NF butane, tetrakis to hexakis (NF furan may be used as CNF oxidizers.

Typical rocket propellant formulations contain 20 to 30% of CNF oxidizer, 30 to 40% of oxygen oxidizer, 2 to 10% powdered metal, and 20 to 40% of the high energy binder to obtain solid propellant composites having specific impulse values in the range of 270 to 300.

Fortunately the liquid CNF oxidizers are compatible with the olyalkyleneamine nitroformates and act as plasticizers thereof.

Various stabilizers may be admixed in small amounts.

What is claimed is:

1. Polyalkyleneamine nitroformate.

2. Polyalkyleneamine nitroformate characterized by polymers containing in each recurring monomeric unit 1 to 4 C atoms, 1 to 4 N atoms with attached 1 to 4 HC(NO moieties.

3. Polyvinylamine nitroformate having the recurring unit:

' 4i 4. Polyethyleneimine nitroformate having the recurring unit:

(CHzCH2N) HC(NO2)a 5. Polyethylenehydrazine nitroformate having the recurring unit:

NHz-H z)a 6. Polybutyleneamine nitroformate having the recurring unit:

CHgNHg-HC(NOz)s (CHz )n CH2NH2-IIC(N0z)3 wherein the subscript 11 indicates a number of said units linked together.

7. Polypropyleneamine nitroformate having the recurring unit:

CH2NH2'HC(NO2)3 (oH -0H--)n wherein the subscript it indicates a number of said units linked together.

8. The method of preparing a high-energy polymer which comprises reacting a polyalkenylamine containing 1 to 4 C atoms and 1 to 4 N atoms in its recurring unit with HC(NO 9. The method of claim 8 in which the polyalkenylamine is reacted with HC(NO in aqueous liquid to form a solid precipitate of nitroformate salt of the polyalkenylamine.

References Cited UNITED STATES PATENTS 10/1967 Beach et al 260-94.7 11/1967 Guthrie 260-583 

1. POLYALKYLENEAMINE NITROFORMATE. 